supplementary materials
3,3,6,6-Tetrakis(hydroxymethyl)-1,2,4,5-tetrazinane tetrahydrate
Dihydroxyacetone (0.90 g, 10 mmol) and hydrazine hydrate (0.49 ml, 10 mmol) in
ethanol (50 ml) were heated for 12 h. Slow evaporation of the solvent gave
colourless crystals in 80% yield. The formulation of the organic molecule was
established by 1H and 13C NMR as well as by mass spectroscopies.
The amino and water H-atoms were located in a difference Fourier map, and
were refined with a distance restraint of N-H = O-H = 0.85 (1) Å; their
Uiso parameters were freely refined. Carbon-bound H-atoms were placed in
calculated positions (C-H = 0.97 Å) and were included in the refinement
in the riding model approximation, with Uiso(H) set to
1.2Ueq(C). The highest peak and the deepest hole are located
0.73 and 0.58 Å from O1W. Although the displacement parameters of
atom O1W are relatively large, no disorder is expected as its H-atoms could
be located and refined.
Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2009).
3,3,6,6-Tetrakis(hydroxymethyl)-1,2,4,5-tetrazinane tetrahydrate
top
Crystal data top
| C6H16N4O4·4H2O | Z = 1 |
| Mr = 280.29 | F(000) = 152 |
| Triclinic, P1 | Dx = 1.371 Mg m−3 |
| Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
| a = 6.3067 (1) Å | Cell parameters from 6318 reflections |
| b = 7.0317 (2) Å | θ = 3.1–40.2° |
| c = 8.4015 (2) Å | µ = 0.12 mm−1 |
| α = 71.010 (1)° | T = 296 K |
| β = 74.424 (1)° | Cube, colourless |
| γ = 85.055 (1)° | 0.40 × 0.40 × 0.40 mm |
| V = 339.36 (1) Å3 | |
Data collection top
Bruker SMART APEXII
diffractometer | 3630 reflections with I > 2σ(I) |
| Radiation source: fine-focus sealed tube | Rint = 0.018 |
| graphite | θmax = 40.2°, θmin = 3.1° |
| φ and ω scans | h = −11→11 |
| 10198 measured reflections | k = −12→12 |
| 4231 independent reflections | l = −15→15 |
Refinement top
| Refinement on F2 | Primary atom site location: structure-invariant direct methods |
| Least-squares matrix: full | Secondary atom site location: difference Fourier map |
| R[F2 > 2σ(F2)] = 0.042 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.137 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.01 | w = 1/[σ2(Fo2) + (0.0853P)2 + 0.0377P]
where P = (Fo2 + 2Fc2)/3 |
| 4231 reflections | (Δ/σ)max = 0.001 |
| 114 parameters | Δρmax = 0.93 e Å−3 |
| 8 restraints | Δρmin = −0.63 e Å−3 |
Crystal data top
| C6H16N4O4·4H2O | γ = 85.055 (1)° |
| Mr = 280.29 | V = 339.36 (1) Å3 |
| Triclinic, P1 | Z = 1 |
| a = 6.3067 (1) Å | Mo Kα radiation |
| b = 7.0317 (2) Å | µ = 0.12 mm−1 |
| c = 8.4015 (2) Å | T = 296 K |
| α = 71.010 (1)° | 0.40 × 0.40 × 0.40 mm |
| β = 74.424 (1)° | |
Data collection top
Bruker SMART APEXII
diffractometer | 3630 reflections with I > 2σ(I) |
| 10198 measured reflections | Rint = 0.018 |
| 4231 independent reflections | θmax = 40.2° |
Refinement top
| R[F2 > 2σ(F2)] = 0.042 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.137 | Δρmax = 0.93 e Å−3 |
| S = 1.01 | Δρmin = −0.63 e Å−3 |
| 4231 reflections | Absolute structure: ? |
| 114 parameters | Flack parameter: ? |
| 8 restraints | Rogers parameter: ? |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top| | x | y | z | Uiso*/Ueq | |
| O1 | 0.62982 (10) | 0.32676 (8) | 0.59353 (6) | 0.03101 (11) | |
| O2 | 0.12442 (8) | −0.12559 (9) | 0.85708 (8) | 0.03186 (11) | |
| O1W | 0.74166 (12) | 0.53141 (12) | 0.78141 (13) | 0.0496 (2) | |
| O2W | 0.81111 (10) | 0.46492 (8) | 0.23874 (7) | 0.03194 (11) | |
| N1 | 0.35398 (7) | 0.15628 (7) | 0.93656 (6) | 0.01863 (8) | |
| N2 | 0.53643 (7) | −0.16882 (6) | 0.93673 (6) | 0.01882 (8) | |
| C3 | 0.30946 (11) | −0.01190 (10) | 0.73791 (8) | 0.02651 (11) | |
| H3A | 0.2599 | 0.1154 | 0.6697 | 0.032* | |
| H3B | 0.3856 | −0.0844 | 0.6586 | 0.032* | |
| C1 | 0.67667 (9) | 0.13379 (9) | 0.69956 (7) | 0.02297 (10) | |
| H1A | 0.7819 | 0.1472 | 0.7609 | 0.028* | |
| H1B | 0.7435 | 0.0517 | 0.6262 | 0.028* | |
| C2 | 0.46871 (8) | 0.02767 (7) | 0.83271 (6) | 0.01806 (9) | |
| H1O | 0.661 (3) | 0.409 (2) | 0.640 (2) | 0.051 (4)* | |
| H2O | 0.140 (3) | −0.2396 (16) | 0.839 (2) | 0.052 (4)* | |
| H1W1 | 0.8827 (15) | 0.535 (3) | 0.765 (2) | 0.057 (4)* | |
| H1W2 | 0.688 (3) | 0.6353 (19) | 0.810 (2) | 0.055 (4)* | |
| H2W1 | 0.753 (2) | 0.430 (2) | 0.3464 (12) | 0.053 (4)* | |
| H2W2 | 0.754 (3) | 0.5766 (18) | 0.198 (3) | 0.069 (5)* | |
| H1N | 0.2237 (14) | 0.1097 (17) | 0.9941 (14) | 0.026 (2)* | |
| H2N | 0.4192 (16) | −0.2420 (16) | 0.9932 (15) | 0.027 (2)* | |
Atomic displacement parameters (Å2) top| | U11 | U22 | U33 | U12 | U13 | U23 |
| O1 | 0.0395 (3) | 0.0239 (2) | 0.02234 (19) | −0.00194 (17) | −0.00506 (17) | 0.00069 (15) |
| O2 | 0.02304 (19) | 0.0353 (2) | 0.0423 (3) | −0.00251 (16) | −0.00474 (17) | −0.0211 (2) |
| O1W | 0.0348 (3) | 0.0488 (4) | 0.0794 (6) | 0.0026 (3) | −0.0098 (3) | −0.0437 (4) |
| O2W | 0.0353 (2) | 0.0254 (2) | 0.0306 (2) | 0.00639 (17) | −0.00462 (18) | −0.00747 (17) |
| N1 | 0.01946 (16) | 0.01761 (16) | 0.01842 (16) | 0.00258 (12) | −0.00506 (12) | −0.00561 (12) |
| N2 | 0.02248 (17) | 0.01557 (15) | 0.01876 (16) | 0.00090 (12) | −0.00525 (12) | −0.00611 (12) |
| C3 | 0.0297 (2) | 0.0293 (3) | 0.0242 (2) | −0.00180 (19) | −0.01135 (18) | −0.00917 (19) |
| C1 | 0.0244 (2) | 0.0221 (2) | 0.01861 (18) | −0.00032 (16) | −0.00180 (15) | −0.00427 (15) |
| C2 | 0.02086 (18) | 0.01704 (17) | 0.01609 (16) | 0.00065 (13) | −0.00472 (13) | −0.00510 (13) |
Geometric parameters (Å, °) top
| O1—C1 | 1.4169 (7) | N1—H1N | 0.86 (1) |
| O1—H1O | 0.851 (9) | N2—N1i | 1.4441 (6) |
| O2—C3 | 1.4198 (9) | N2—C2 | 1.4724 (6) |
| O2—H2O | 0.86 (1) | N2—H2N | 0.87 (1) |
| O1W—H1W1 | 0.86 (1) | C3—C2 | 1.5305 (8) |
| O1W—H1W2 | 0.86 (1) | C3—H3A | 0.97 |
| O2W—H2W1 | 0.84 (1) | C3—H3B | 0.97 |
| O2W—H2W2 | 0.84 (1) | C1—C2 | 1.5382 (7) |
| N1—N2i | 1.4441 (6) | C1—H1A | 0.97 |
| N1—C2 | 1.4712 (7) | C1—H1B | 0.97 |
| | | |
| C1—O1—H1O | 105.1 (11) | C2—C3—H3B | 109.4 |
| C3—O2—H2O | 104.1 (11) | H3A—C3—H3B | 108.0 |
| H1W1—O1W—H1W2 | 107.6 (16) | O1—C1—C2 | 112.12 (5) |
| H2W1—O2W—H2W2 | 105.0 (18) | O1—C1—H1A | 109.2 |
| N2i—N1—C2 | 113.59 (4) | C2—C1—H1A | 109.2 |
| N2i—N1—H1N | 106.4 (8) | O1—C1—H1B | 109.2 |
| C2—N1—H1N | 110.2 (8) | C2—C1—H1B | 109.2 |
| N1i—N2—C2 | 113.72 (4) | H1A—C1—H1B | 107.9 |
| N1i—N2—H2N | 107.4 (8) | N1—C2—N2 | 114.01 (4) |
| C2—N2—H2N | 108.2 (8) | N1—C2—C3 | 107.44 (4) |
| O2—C3—C2 | 111.33 (5) | N2—C2—C3 | 107.54 (4) |
| O2—C3—H3A | 109.4 | N1—C2—C1 | 110.36 (4) |
| C2—C3—H3A | 109.4 | N2—C2—C1 | 107.54 (4) |
| O2—C3—H3B | 109.4 | C3—C2—C1 | 109.89 (4) |
| | | |
| N2i—N1—C2—N2 | 47.54 (6) | O2—C3—C2—N1 | −65.11 (6) |
| N2i—N1—C2—C3 | 166.60 (4) | O2—C3—C2—N2 | 58.02 (6) |
| N2i—N1—C2—C1 | −73.60 (5) | O2—C3—C2—C1 | 174.80 (5) |
| N1i—N2—C2—N1 | −47.60 (6) | O1—C1—C2—N1 | −54.32 (6) |
| N1i—N2—C2—C3 | −166.60 (4) | O1—C1—C2—N2 | −179.24 (4) |
| N1i—N2—C2—C1 | 75.09 (5) | O1—C1—C2—C3 | 63.98 (6) |
| Symmetry codes: (i) −x+1, −y, −z+2. |
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H1O···O1W | 0.85 (1) | 1.87 (1) | 2.704 (1) | 166 (2) |
| O2—H2O···O2Wii | 0.86 (1) | 1.87 (1) | 2.723 (1) | 171 (2) |
| N1—H1N···O2iii | 0.86 (1) | 2.23 (1) | 3.036 (1) | 155 (1) |
| N2—H2N···O1Wi | 0.87 (1) | 2.36 (1) | 3.130 (1) | 148 (1) |
| O1W—H1W1···O2Wiv | 0.86 (1) | 1.92 (1) | 2.782 (1) | 172 (2) |
| O1W—H1W2···N2v | 0.86 (1) | 2.03 (1) | 2.869 (1) | 166 (2) |
| O2W—H2W1···O1 | 0.84 (1) | 1.92 (1) | 2.759 (1) | 175 (2) |
| O2W—H2W2···N1vi | 0.84 (1) | 2.02 (1) | 2.853 (1) | 171 (2) |
| Symmetry codes: (ii) −x+1, −y, −z+1; (iii) −x, −y, −z+2; (i) −x+1, −y, −z+2; (iv) −x+2, −y+1, −z+1; (v) x, y+1, z; (vi) −x+1, −y+1, −z+1. |
Table 1
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H1O···O1W | 0.85 (1) | 1.87 (1) | 2.704 (1) | 166 (2) |
| O2—H2O···O2Wi | 0.86 (1) | 1.87 (1) | 2.723 (1) | 171 (2) |
| N1—H1N···O2ii | 0.86 (1) | 2.23 (1) | 3.036 (1) | 155 (1) |
| N2—H2N···O1Wiii | 0.87 (1) | 2.36 (1) | 3.130 (1) | 148 (1) |
| O1W—H1W1···O2Wiv | 0.86 (1) | 1.92 (1) | 2.782 (1) | 172 (2) |
| O1W—H1W2···N2v | 0.86 (1) | 2.03 (1) | 2.869 (1) | 166 (2) |
| O2W—H2W1···O1 | 0.84 (1) | 1.92 (1) | 2.759 (1) | 175 (2) |
| O2W—H2W2···N1vi | 0.84 (1) | 2.02 (1) | 2.853 (1) | 171 (2) |
| Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x, −y, −z+2; (iii) −x+1, −y, −z+2; (iv) −x+2, −y+1, −z+1; (v) x, y+1, z; (vi) −x+1, −y+1, −z+1. |
The authors acknowledge support from Chulalongkorn University and the Center of
Excellence for Petroleum, Petrochemicals and Advanced Materials of Thailand.
Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.
Bruker (2005). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Skorianetz, W. & Kovats, E. Sz. (1970). Helv. Chim. Acta, 53, 251–262.
Sun, Y.-Q., Hu, W.-X. & Yuan, Q. (2003). Synth. Commun. 33, 2769–2775.
Westrip, S. P. (2009). publCIF. In preparation.
Zhou, M., Cai, Z.-B., Yang, Z.-Y. & Hu, W.-X. (1999). Jingxi Huagong, 16, 1–4.
O, O-H![[Figure 1]](./ci2961fig1thm.gif)
